Vax and sulphur dyestuff



Patented Aug. 1, 1933 VAT AND SULPHUR DYESTUFF PREPARATION Hermann Berthold and Herman Friedrich, Leverkusen-on-the-Rhine, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a Corporation of Delaware No Drawing. Application December 3, 1931, serigloNo. 578,847, and in Germany December 8 Claims. (01 H.)

The present invention relates to new vat and products are printed in the customary manner, sulphur dyestuif preparations for textile printthe printings are steamed, for example, .in a Mather Platt apparatus and developed an In accordance with the invention vat and sulfinished in the customary manner.

phur dyestufi. preparations are produced com- When the above printing colors contain salts prising watersoluble salts of the products of the of the products of the reaction of carbocyclic reaction of halogen fatty acids and carbocyclic aromatic hydroxy compounds and halogen fatty aromatic hydroxy compounds of the following acids, (which products may likewise replace formula: R.O.R1.COOH wherein R means a carwholly or in part the glycerine or the sodium bocyclic aromatic nucleus and R1 means an alisalt of benzyl sulphanilic held), there are ob- 65 phatic radical.' 1 ,tained stronger printings and better fixation- The new preparations are employed for the than without these materials.

printing or slop-padding of textiles, such was cot- The process of printing with previous reducton, wool, cellulose acetate silk and the like. tion is used principally for dyestuffs, which vat They are distinguished by considerable advane with difiiculty and when applying the dyestuffs 70 tages' over the preparations hitherto known for in the form of a powder. Endeavours are howthe said purpose. Thus, according to the inever made to replace this process even in the Ventieh pastes can be p e which, SD latter cases by process 2 (below).

i y wh n nin in i i n g y rin or, 2. Process of printing without previous reanother similar polyvalent alcohol miscible with a ction, The following is an example of the 75 water, such as for example, ethylene glycol, diprocess:- ethyleneglyeol, thiodiglyeol d th k a of A printing color is made up from:-10-20 particular t ili y, do n t f rm dep s r grams of dyestufi paste, 0-10 grams of water, and crusts andvdo not freeze or only freeze at a very 30 grams of a thickening agent, containing in w' p th r the prepara- 1000 parts by weight.170 arts b weight of ions con i h mp n sp ifi w n tragacanth 65:1000, 160 parts by weight of inus d f print n or sl p-paddin e sure in t dustrial gum 1:1, 60 parts by weight of wheat as a p v fixing and Stronger printingstarch, 150 parts by weight of water, 60 parts than the rr p ndin p p a n not by weight of British gum, 100 parts by weight of tain t additions in qu In t presglycerine, 150'parts by weight of potassium carnt process o y ch p u y ufi give good bonate and 150 parts by weight of sodium formresults, which possess an aflinity for textile fibres aldehyde. su1phoxy1ate i Wh app for p h D P Textile products printed with such printing The extent of the efiect attainable does not colors are Steamed in ordr to develop the dyeonly depend n the nature of the dyestufi stuff then oxidized and finished in the custoployed and on the compounds used as additions, mary n but also on the method by which the Printing When the above printing colors contain, colors are produced from the dyestuff prepara- K for example, the sodium salt of one of the tlons, and on the speclah methods of known cresoxy acetic acids of the formula 40 The printing m o Principally'concemed can CH3CsH4O.CH2.COOH, the printings in accord- 95 be divided into two groups:-

1. Process of printing with previous reduction own process), for examplez-40-200 grams 0 dyestufi (in paste) are pasted with 50 grams g l g g ggi g gg 332 5 i o g given satisfactory results only in the first process.

grams of calcined sodium carbonate and 500450 This fact constitutes a considerable technical adgrams of a thickening agent containing in 1000 Vance particularly in the avoidance of caustic alparts by weight:-280 parts by weight of ti kalies, in consequence whereof the fibre is more gum, parts by weight of starch, 20 parts by cautiously treated, furthermore, 1n the prolonged weight of the sodium salt of benzyl sulphanilic ability and app y of the made HP Print; acid and 600 parts by weight of water, and at ing pastes in consequence of the absence of the 70 C. 4090 grams of sodium formaldehyde sulreadily decomposable hydrosulphite, which is enphoxylate and 10-40 grams of sodium hydrosultirely replaced by sodiumformaldehyde sulphox- 55 phite are added. with this printing color textile ylate. I

ance with this process are usually stronger and better fixed than without this addition. Consequently it is possible to print by this latter process also such dyestuifs, as have hitherto It should be expressly mentioned that these two main groups of printing methods are likely to be applied with success in most cases, however, modifications of these processes are also applicable.

The addition of the salts of the condensation, products of carbocyclic aromatic hydroxy compersion of the dyestuff. When the dyestuif pastes contain more water than is desired, they can be concentrated, for example, by evaporation.

Thus are obtained uniform, smooth pastes, which do not dry up, do not form encrustations, do not deposit, do not freeze and, even after a prolonged period, can still be worked up to valuable printing colors, especially, when a preserving agent is also added to the pastes.

(b) The dyestuif is finely ground and intimately mixed with the likewise finely ground addition in question. The addition of an emulsifying agent may be of advantage.

(c) The dyestuff in the form of a pressed cak containing water or in the form of an aqueous paste is evaporated to dryness in the presence of the assistant compound to be added and, if desired, in the presence of dextrine or an emulsifying agent.

(d) The dyestufi is reduced in the presence of glycerine or of another similar .polyhydric alcohol miscible with water, for example, thiodiglycol,

containing in, 1000 parts by weight:--60 parts by weight of wheat starch, 150 parts by weight of water, 60. parts by weight of British gum, 260

parts by weight of industrial gum 1: 1, 170 parts by weight of tragacanth 65: 1000, 150 parts by weight of potassium carbonate and 150 parts by weight of sodium formaldehyde sulphoxylate are stirred to a printing color with the aqueous dyestuff paste and 4 grams of glycerine and 4 grams of the sodium salt of phenoxy acetic acid.

The dyestuff paste thus made up prints considerablybetter than a paste produced with the same thickening and 8% .of glycerine in the absence of the sodium salt ofphenoxy acetic acid.

In all the instances described under (a) to (e) dyestuif preparations are obtained, which either as such possess technical advantages '(see, for example, the preparations under (41)), or as contrasted with the same preparations without the addition of the new compounds display improved qualities of printing and fixation.

'The amount of the reaction products of carbocyclic aromatic hydroxy compounds with halogen fattty acids to be added may vary within the widest limits. Generally, we prefer to apply about 25-100% by weight of the same, (calculated on the dyestufi present) to get the best results,

but smaller or larger amounts are likewise operable.

It may be mentioned that the reaction products in question can be prepared, for example,'by reacting with a halogen fatty acid upon a carbothese compounds as still contain oxygen in the meso-position. By these additions the printing qualities of the new preparations are in many instances still further improved.

The term hydrotropically acting substances indicates such substances which in aqueous solu tions show theeapability of dissolving other substances which per so are insoluble or diflicultly soluble in water (compare Neuberg, Biochem. Zeitschrift, vol. 76, 1916, pp. 107-176, reported in Chem. Zentralblatt, 1916, pp. 970-971).

It is pointed out that the expression vat and sulphur dyestuff preparations for textile printing is intended to include all preparations specified under (a) to (e) and preparations similar thereto, which can find application for printing purposes and contain salts, for example, alkali metal salts (including ammonium salts), of the products of the reaction of halogenated fatty acids and carbocyclic aromatic hydroxy compounds.

The printing methods, which can be used with advantage, have already been considered. The development of the printings can be carried out by the customary processes, for example, in the following manner: After drying the printed material the same is subjected to the action of moist steam and the dyestuif is developed by means of potassium chromate/acetic acid (2 grams of K2C12O7 and 5 cos. of 30% aceticacid in 1 litre of water), followed by soaping at the boil.

The following examples illustrate the invention without limiting it thereto.

Example 1 A printing color of 6.6'-diethoxy 2.2'-bis-thionaphthene-indigo, produced in the manner de-' scribed under (e), and in which the sodium salt of phenoxy acetic acid may be replaced by that of 'ortho-, meta-, or para-creso'xy acetic acid or derivatives of these acids, yields printings, which fix considerably better and are more vivid and stronger than those obtainable by the corre- Example 2 The dyestuff of Examplel can be replaced by that obtainable in accordance with Example 1 of U. S. Patent 888,852 from naphthohydroxythiophen carboxylic acid, or by the dyestuif from 6-methoxy-3-hydroxythionaphthene and 4- methyl 6 bromol 2.3 -dihydro-3 -keto -thionaphtheme-2-(para-dimethylamino)-anile, or by the dyestuff of the following constitution:-

or by the dyestuif referred to in the Colour Indexunder N0. 1101 (Caledon Jade Green), or by the dyestuff obtainable in accordance with the German Patent 242,621 from nitro-methyl-benzanthrone and sulphur, or. by 3.4-dichloro-1.2- anthraquinoneacridone, or by 6.6-dichloro4.4- dimethylbisthionaphthene indigo, or by the dye.- stufi obtainable from 4.6-climethyl-5.7-dichloroisatine with chlorinated alpha-naphthol, or by tetra-bromoindigo, brominated anthanthrones or dichloro-indanthrone.

- Other dyestuffs of the anthraquinonoid and indigoid series and also sulphur dyestuffs can be applied with advantage in accordance with the above example.

Furthermore, the sodium salts of the phenoxy or cresoxy acetic acid can be replaced by the salts of other products of the reaction of halogen fatty acids (beta-chloro-propionic acid, chloro-butyric acids or halogen fatty acids with branched or longer chains,,such as chloro stearic acid etc.) and other aromatic hydroxy compounds (alphaor beta-naphthol, chloro-phenols, nitrophenols, halogen-, nitroor alkyl-naphthols, dior polyhydroxybenzenes or -naphthalenes, such as resorcin, brenzcatechin, 1.5- or 1.8-dihydroxynaphthalene, trihydroxybenzenes, hydroxyanthracenes etc.).

Instead of the sodium salts other water soluble salts especially alkali metal salts (which term is intended to include ammonium salts) may obviously be used.

We claim:

11 Vat and sulphur dyestuiT preparations for textile printing comprising a water-soluble salt of an acid of the probable formula: R.O.R1COOI-I wherein R means a carbocyclic aromatic nucleus and R1 means an aliphatic radical.

2. Vat and sulphur dyestufi pastes for textile printing comprising a polyvalent alcohol miscible with water and an alkali metal salt of an acid of the probable formula: R.O.R1COOI-I wherein R means a carbocyclic aromatic nucleus and R1 means an aliphatic radical.

3. Vat dyestuff preparations for textile printing comprising an alkali metal salt of an acid of the probable formula: R.O.R1.COOH wherein R means a carbocyclic aromatic nucleus and R1 means an aliphatic radical, in an amount between about 25-100 per cent by weight of the vat dyestufi applied.

4. Vat dyestuif pastes for textile printing comprising a polyvalent alcohol miscible with water and an alkali metal salt of an acid of the probable formula, R.O.R1.COOH wherein R means a carbocyclic aromatic nucleus and R1 means an aliphatic radical, in an amount between about 25-100 per cent by weight of the vat dyestufit' applied.

5. Vat dyestufi' pastes for textile printing comprising an alcohol of the group consisting of glycerine and ethylene glycol and an alkali metal salt of an acid of the probable formula: R.O.R1.COOH wherein R-means a carbocyclic aromatic nucleus and R1 means an aliphatic radical, in an amount between about 25-100 per cent by weight of the vat dyestufi applied.

6. Vat dyestuff preparations for textile printing comprising a compound of the-group consisting of the alkali metal salts of phenoxy acetic acid and the cresoxy acetic acids.

7. Vat dyestufi pastes for textile printing com- 135 prising an alcohol of the group consisting of glycerine and ethyleneglycol and a compound of the group consisting of the alkali metal salts of phenoxy acetic acid and the cresoxy. acetic acids in an amount between about 25-100% by weight of the vat dyestuff applied.

8. Vat dyestuff preparation for textile printing comprising the dyestufi of the probable formula:-

and a compound of the group consisting of alkali metal salts of phenoxy acetic acid and cresoxy acetic acids in an amount between about 25-100% by weight of the vat dyestuff applied.

HERMANN BERTHOLD. HERMANN FRIEDRICH. 

